Chemical Engineering
Thermodynamics (CB206)
Chemical and Biochemical Engineering
Indian Institute of Technology Patna
Atanu K Metya
[email protected]
Chemical Engineering Thermodynamics
Equations of State and Generalized Correlations
for Prediction of Volumetric Properties of Fluids
Chemical Engineering Thermodynamics
• Phase Rule
•F=C–P+2
• F is the number of degrees of freedom, P is the number of phases, and C
is the number of chemical species present in the system
• How many phase-rule variables must be specified to fix the thermodynamic
state of each of the following systems?
• Liquid water in equilibrium with its vapor.
• Liquid water in equilibrium with a mixture of water vapor and nitrogen.
• A three-phase system of a saturated aqueous salt solution at its boiling
point with excess salt crystals present.
Chemical Engineering Thermodynamics
Phase-change processes of pure substances
• Compressed liquid or a subcooled liquid
• Saturated liquid
• Saturated Vapor and Superheated Vapor
• Saturated liquid–vapor mixture
Chemical Engineering Thermodynamics
• Saturation Temperature (Tsat): at a given pressure,
the temperature at which a pure substance changes
phase
• Saturation Pressure (Psat): at a given temperature,
the pressure at which a pure substance changes phase
Chemical Engineering Thermodynamics
• Latent heat
• Latent heat of fusion
• Latent heat of vaporization
• At 1 atm. pressure, the latent heat of fusion of water is 333.7 kJ/kg and the
latent heat of vaporization is 2256.5 kJ/kg
Chemical Engineering Thermodynamics
• Liquid–vapor saturation curve.
Chemical Engineering Thermodynamics
The T-v Diagram for a pure
substance
• Critical point: the saturated
liquid and saturated vapor states
are identical
• The critical-point properties of
water are
• Pcr = 22.06 MPa,
• Tcr = 373.95°C
• vcr = 0.003106 m3/kg.
Chemical Engineering Thermodynamics
• The T-v Diagram
• Saturated liquid line
• Saturated vapor line
• Compressed liquid region
• Superheated vapor region
• Saturated liquid–vapor mixture
region or the wet region
Chemical Engineering Thermodynamics
• The P-v Diagram
Chemical Engineering Thermodynamics
• PV diagrams for a pure substance
Chemical Engineering Thermodynamics
PT Behavior of Pure
Substances
• Sublimation curve
• Fusion curve
• Vaporization curve
• Critical point
• Phase diagram
Chemical Engineering Thermodynamics
Saturated Liquid and Saturated Vapor States
Chemical Engineering Thermodynamics
Saturated Liquid and Saturated Vapor States
Chemical Engineering Thermodynamics
Chemical Engineering Thermodynamics
Chemical Engineering Thermodynamics
Chemical Engineering Thermodynamics
Chemical Engineering Thermodynamics
Saturated Liquid and Saturated Vapor States
• A rigid tank contains 50 kg of saturated liquid water at 90°C. Determine
the pressure in the tank and the volume of the tank.
• A piston–cylinder device contains 2 ft3 of saturated water vapor at 50-psia
pressure. Determine the temperature and the mass of the vapor inside the
cylinder.
• A mass of 200 g of saturated liquid water is completely vaporized at a
constant pressure of 100 kPa. Determine (a) the volume change and (b) the
amount of energy transferred to the water.
Chemical Engineering Thermodynamics
• Saturated Liquid–Vapor Mixture
• Quality (x): the ratio of the mass of vapor to the total mass of the mixture
Chemical Engineering Thermodynamics
• A rigid tank contains 10 kg of water at 90°C. If 8 kg of the water is in the
liquid form and the rest is in the vapor form, determine (a) the pressure in
the tank and (b) the volume of the tank.
• An 80-L vessel contains 4 kg of refrigerant-134a at a pressure of 160 kPa.
Determine (a) the temperature, (b) the quality, (c) the enthalpy of the
refrigerant, and (d) the volume occupied by the vapor phase.
Chemical Engineering Thermodynamics
Chemical Engineering Thermodynamics
• Properties of saturated ice–water vapor mixtures
Chemical Engineering Thermodynamics
• Properties of saturated ice–water vapor mixtures
Chemical Engineering Thermodynamics
Superheated Vapor
Compared to saturated vapor, superheated vapor is characterized by
• Lower pressures (P < Psat at a given T)
• Higher temperatures (T > Tsat at a given P)
• Higher specific volumes (v > vg at a given P or T)
• Higher internal energies (u > ug at a given P or T)
• Higher enthalpies (h > hg at a given P or T)
Chemical Engineering Thermodynamics
Chemical Engineering Thermodynamics
Chemical Engineering Thermodynamics
Chemical Engineering Thermodynamics
Chemical Engineering Thermodynamics
• One pound-mass of water fills a 2.29-ft3 rigid container at an initial
pressure of 250 psia. The container is then cooled to 100°F. Determine the
initial temperature and final pressure of the water.
• Determine the temperature of water at a state of P = 0.5 MPa and h = 2890
kJ/kg.
Chemical Engineering Thermodynamics
Compressed Liquid
• In the absence of compressed liquid data, treat compressed liquid as a
saturated liquid at the given temperature
• In general, a compressed liquid is characterized by
• Higher pressures (P > Psat at a given T)
• Lower temperatures (T < Tsat at a given P)
• Lower specific volumes (v < vf at a given P or T)
• Lower internal energies (u < uf at a given P or T)
• Lower enthalpies (h < hf at a given P or T)
Chemical Engineering Thermodynamics
Chemical Engineering Thermodynamics
Chemical Engineering Thermodynamics
Chemical Engineering Thermodynamics
Chemical Engineering Thermodynamics
• Determine the internal energy of compressed liquid water at 80°C and 5
MPa, using (a) data from the compressed liquid table and (b) saturated
liquid data. What is the error involved in the second case?
• Determine the missing properties and the phase descriptions in the
following table for water:
Chemical Engineering Thermodynamics